Treatment of wool and products therefor



Patented Apr. 12, 1949 TREATMENT ()F WOOL AND PRODUCTS THEREFOR John B.Rust, East Hanover, N. .L, assignor to Montclair Research Corporation, acorporation of New Jersey No Drawing.

Claims. 1

The present invention relates to the treatment and shrinkproofing ofwool and wool containing fibers, to the methods for obtaining suchtreated and shrinkproofed fibers, to the materials and productsresulting from such processes and treatments, and to the baths andmaterials utilized to accomplish these results as well as methods ofpreparing such baths and materials.

Urea formaldehyde type resins under which there may be included suchsynthetic resins as monoor di-methylol urea or mixtures thereof,

urea formaldehyde or alkylated urea formaldehyde condensation products,melamine formaldehyde resins and their alkylated modifications, such asfor instance, the types known to the trade as Lanaset or Resloom, havebeen utilized in the treatment of textiles and fabrics for the purposeof crease-proofing or improving draping qualities of fabrics andtextiles. Such agents are very inferior as shrinkproofing agents forwool and have little effect per se on such shrinkproofing unless curedat high temperature, but such control is usually accompanied by a degreeof harshening of the fabric.

In prior applications more particularly identified below, the art hasbeen taught that butadime-1.3 and some of its copolymers producesuperior shrinkproofing effects on wool and related materials. In somecases there is a slight sticky or greasy hand imparted to the goodswhich may be objectionable depending on the particular utilities forwhich the materials are employed.

Among the objects of the present invention is the treatment of wool andwool containing materials to render the treated material substantiallyresistant to fulling, felting, or shrinking without damage to the fabricor fibers, and at the same time preserving the desirable hand of suchmaterials as well as retaining favorable wearing qualities.

Other objects of the present invention include shrinkproofed wool andwool containing fabrics.

Other objects include 'the treatment of wool and wool containingmaterials to improve their draping qualities.

Further objects include the treating baths and materials required forthe purposes set forth above, as well as methods for producing suchmaterials.

Still further objects and advantages of the present invention willappear from the more detailed description set forth below, it beingunderstood that this more detailed description is given by way ofillustration and explanation only, and

not by way of limitation, since various changes therein may be made bythose skilled in the art without departing from the scope and spirit ofthe present invention.

In accordance with the present invention, the wool or wool containingfibers, which may be of Application September 3,1946, Serial No. 694,675

various types, is treated with an emulsion more particularly an aqueousemulsion or dispersion, of a synthetic butadiene-1.3 polymer orcopolymer in combination with aqueous solutions or dispersions ofsynthetic resins, such asfor instance, monoor di-methylol urea ormixtures thereof, urea formaldehyde or alkylated urea formaldehydecondensation products, melamine formaldehyde resins or their alkylatedmodifications, such as for instance, the types known to the trade asLanaset" or Resloom."

It has been found that the combination of these two classes of materialsnot only improves the hand of the goods, but also quite unpredictablythat certain unexpected improvements in the shrinkproofingcharacteristics accrue and there are also additional important qualitiesobtained such as improved draping, etc.

The wool treated may be of any desired type, such as raw wool, yarn,knitted or felted fabrics, woven or mixed goods, or combination fabricsin-- cluding wool in various ways.

The wool may be treated with the treating emulsions, dispersions orsolutions in any desired way, as by immersing-the wool in the treatingbath, or padding the treating bath on the wool, or

' by exhaustion of the polymer onto the wool, etc.,

various methods being more particularly illustrated below. And thesequence of the application of the resin and polymer components may bealtered depending on the results desired. Thus if a finish is desiredwhich has a certain "tack to it, it may be desirable to treat the goodsfirst with the resin and then with the polymer. 0n the other hand, if astiffer finish is desired, the procedure may be reversed, first treatingthe goods with the polymer and then with the resin. 01 combinations maybe employed in which the treating bath includes both the resin and thepolymer. An exceedingly simple and rapid method consists in a paddingoperation whereby both the resin and the elastomeric components areapplied simultaneously from the same bath, followed by the requiredamount of curing. Where the treatment is carried out by successiveapplicatreatment with resin with or without curing, the

treated material is then subjected to an intermediate step ofacidification or treatment with an acid solution before the applicationof the polymer bath.

Any of the urea formaldehyde type resins under which all of themodifications set forth above are included, may be utilized so that atleast one of the urea formaldehyde and'melamine formaldehyde resins isemployed and in the final product is in cured condition. Such ureaformaldehyde type resins are generally applied in the fabrics, these maybe padded and the excess liquor removed by passing the impregnatedfabric through squeeze rolls. The strength of the pad liquor isdependent upon and determined by the amount of resin which it is desiredto deposit on the fabric, as well as by the amount of liquid pick-up ofwhich the fabric is capable.

The amount of resin applied to the goods is determined by the desiredeffect but will be generally limited between 1 and 25% on the weight ofthe fabric treated. A suitable curing catalyst such as ammoniumphosphate, ammonium sulfate, etc.,'is desirably added to the solutioncontaining the resin in order to facilitate. curing. The fabric may thenbe dried at any suitable drying temperature ranging between roomtemperature and 100 C. and then cured. Altematively, the fabric may beexposed to the curing temperature at once. The curing temperature, aswell as the time required to complete the cure differs for variousresins, and is conditioned also by the presence, quantity and kind ofcatalyst used. The curing temperature may vary between room temperatureand 150 C. and the time required may range from 5 minutes to severaldays. It is important to note that materials may be employed which cureat room temperatures in reasonable periods of time so that ele-. vatedtemperatures and long periods of treatment are not essential but may beemployed.

The butadiene-1.3 polymer or copolymer-may be applied to the fabric invarious ways. Thus the aqueous polymeric dispersion may be diluted to.such an extent that the finished fabric will contain from 1 to 25% ofthe polymer. The goods are simply padded through this liquor or thematerial is treated by immersion. The excess liquor is removed either bysqueezing or by centrif-ugal extraction. The bath may be conditionedwith ammonia, wetting agents including long chain alcohol sulfates suchas sodium lauryl sulfate, soaps and the like. In some cases it may beboth possible and advisable to adjust the pH of the pad liquor below 7in order to cause partial agglomeration, using acetic acid, sulfuricacid, phosphoric acid and the like, for this purpose. After padding, itis only necessary to dry the fabric at any desired temperature in orderto set the polymer, that is, to form a stable bond between it and thefiber. On the other hand, the dispersion may be discharged on the fiberfrom a suitable bath, such a bath consisting essentially of an aqueousdilution of the polymeric dispersion to which has been added suitableconditioning electrolytes and the pH of which has been adjusted below 7,such a bath being stable at room temperatures unless in contact withreceptive fibers. As such conditioning electrolytes, water-soluble saltsmay be used. The treatment is carried out by immersing the fibers orfabrics in this bath until exhaustion is complete. The temperature ofthe bath may be at room temperature but more desirably is kept between40 C. and boiling. The rate of exhaustion is regulated by thetemperature as well as by the concentration of the electrolytes. hascleared up substantially'or completely, the goods may be removed, rinsedand dried.

In application Serial No. 537,537, filed May 26, 1944, now Patent2,447,538, of which the present application is a continuation-in-part,and in After the bathdo not precipitate the polymer.

which there is more particularly claimed the shrinkproofing of wool bythe utilization of aqueous baths containing a synthetic butadienepolymer, an emulsifying agent and a conditioning electrolyte, the bathdesirably having apH below 7, there is disclosed the utilization ofbutadiene polymers and polymers of its homologues to give superiornon-felting effects. It has been found that the use of straightbutadiene polymers or butadiene homologue polymers, that is, those inwhich the butadiene or the butadiene homologue is the sole polymer,gives superior nonfelting and wool shrinkproofing than do the hutadienecopolymers. The polymeric butadiene derivatives are those ofbutadiene-1.3 and its lower homologues, such as butadiene-1.3, isoprene,dimethyl butadiene, ethyl butadiene, ethoxy and methoxy butadiene,cyanobutadiene, particularly such derivatives of butadiene-1.3. As thereset forth, copolymers of butadiene or butadiene homologues as set forthabove may be utilized as long as the added component in producing thecopolymer is not present in an amount which interferes with the desiredshrinkproofing effect. Such added copolymerizing maierials include themethacrylates and acrylates, such as methyl methacrylate and vinylcompounds generally including vinyl acetate, methyl methacrylate, ethylacrylate, styrene, acrylo-nitrile, vinyl pyridine, methacrylonitrile,isopropenyl methyl ketone, vinyl phenyl ketone, vinyl methyl ketone. andthe like.

As further set forth in said application, the electrolyte content of thebath emulsion or dispersion may vary over substantial limits butsufficient electrolyte should be present to condition the bath so thatthe bath although stable in the absence of wool fibers, will deposit thepolymer in the presence of the conditioning electrolyte. Generally theelectrolyte content for this purpose will vary between about 25% toabout 5000% based on the weight of polymeric butadiene derivativepresent. As such electrolyte, water-soluble salts may be used, desirablysuch salts which The followin are exemplary: sodium sulfate, sodiumchloride, sodium bromide, sodium iodide, sodium phosphate, sodiumsulfamate, sodium sulfite, sodium bisulfate, sodium bisulfite, sodiumnitrate, sodium acetate, and the like, and similar salts of the otheralkali metal group including those of potassium, lithium, caesium, and'so on. Salts like zinc chloride may also be used where the coagulationdoes not appear to be too serious since it occurs in small particulateform, and the particles may be redispersed by stirring. Neutral salts,specifically salts of strong bases and strong acids, particularlyinorganic salts, are preferred. They may be generally characterized assubstantially neutral highly ionizing salts.

The operation of applying the polymer is desirably carried out attemperatures ranging from 40 C. to the boiling point of the bath. Theprocess may be applied before or after fulling, weaving, scouring andthe like operations. In some cases it may be applied in the dye bath.Mixed goods including wool-cotton, wool-rayon, etc., can be treated bythe methods without any deleterious effect. The wool may be subjected toa pretreatment of any desired type, as for example, chlorination orbromination before being treated; in accordance with the presentinvention.

As further set forth in said prior application, the emulsions containingthe butadiene polymer ass-mes may include any anionic emulsifying agentwhich is stable at a pH below 7. Such emulsifying agents are exemplifiedby sodium lauryl sulfonate.

sodium alkyl naphthalene sulfonates, long chain alkyl sodium sulfonates,sodium dioctyl suliosuc-; cinate. etc. There may also be used neutralnoncationlc emulsifying agents such as mannitol monolaura-te, thereaction product of protein degradation products with acid chlorides,ethylene oxide reaction products with fatty acid, fatty alcohols, andthe like.

As further set forth in said application, the emulsions of the polymerused are desirably but not necessarily, those which have been carried toa 100% polymerization. When 100% polymerization is obtained,considerable cross-linking has occurred in the polymer with consequentinsolubility in organic solvents. Thus a type of prevulcanization of thepolymer has been obtained.

It is also possible to vulcanize the polymers with vulcanizingaccelerators such as thiuram dis-ulfite, etc, vulcanizing agents such assulfur, dinitrobenzene, alkyl phenol sulfide, etc., either previous orsubsequent to deposition or..,dyeing, into the wool fibers.

As pointed out immediately above, th polymer employed is in a conditionin which if deposited from the emulsion or dispersion, the polymer is ina substantially non-tacky condition and gives a non-tacky deposit. It issubstantially insoluble in organic solvents but may be swollen to someextent with such solvents. It is in a condition in which it is totallyunsuitable as synthetic rubher or rubber-like material since ifcoagulated by any suitable means it gives crumbly materials which cannotbe milled on rubber milling equipment and which are entirely composed ofcrosslinked polymers. Any of the polybuta'diene-L3 compositions as setforth in said prior application may be utilized as the component forthis phase of the treatment of the present invention.

While as pointed out in said prior application, straight butadienepolymers and but-adiene homologue polymers are preferred, in order toobtain special effects certain additions and modiiication may be made toa limited extent. These additions may consist of other polymers in theform of emulsions, dispersions, factices, etc., and may includechloroprene polymer, polyvinyl compounds, polyacryl-ates. such aspolyethylacrylate,

1945, entitled Wool treatinB. products and-meth-' ods, now Patent2,447,876, there is more particularly claimed the utilization ofbutadiene polymers in aqueous dispersions where soap is the es- 'sentialor only emulsifying agent present, the pH of the bath being'at least 7and the soap being an alkali salt of a long chain carboxylic acid. Suchbaths and wool treated in accordance therewith may be utilized as thepolymer treatment phase of the present invention.

In application Serial No. 586,637, filedApril 4, 1945, for Pre-shrunkand shrink-proofed wool, there is more particularly described andclaimed the treatment of wool to obtain shrinkproo'fing by theutilizationof butadiene-1.3 emulsions and related materials as set forthabove in which operatiorls'the wool is subjected to a treatment topolyalkylmethacrylates, polystyrene and its derivatives such as alphabeta dimethylstyrene, di-- chlorostyrene, acrylonitrile,methacrylonitrile, etc. While it is understood that the addition ofthese auxiliary substances usually is limited to the extent where nosubstantial interference with the shrinkproofing characteristics isexperienced, in special applications it may be desirable to exceed thoseproportions.

Thus in application Serial No. 563,791, filed November 16, 1944,entitled Treatment of-wool, now Patent 2,447,539, there is moreparticularly claimed the treatment of wool by utilization of--copolymers of a but-adiene-l.3 and a methacrylate ester such as methylmethacryl'ate, ethyl methacrylate, and butyl methacrylate, in aqueousemulsions of the character set forth above, the amount or methacrylatepolymer being about 5 to 20% of the interpolymer, of the ethylmethacrylate being about 5 to 50% of the interpolymer, and of the butylmetha-crylate being from about 5% to 40% of the interpolymer. Any ofsuch materials may be utilized as the polymer component of the presentinvention.

In application Serial No. 586,293, filed April 3,

relax any stretched wool fibers to, produce a preshrunk wool and suchpre-shrinking operations and polymer depositions for shrink-proofing maybe utilized in any order of steps successively or simultaneously. Thoseoperations in connection with the utilization of polymer forshrinkproofing and also pre-shrinking operations may also be employed inaccordance with the present invention.

In application Serial No. 594,585, filed May 18; 1945, entitledInterpolymer treatment of wool, now Patent 2,447,540, there is moreparticularly claimed the treatment of wool utilizing a copolymer ofbutadiene and an acrylate ester, more specifically a methyl acrylate notexceeding 40% of the copolymer, an ethyl acrylate in an amount notexceeding about 50% of the interpolymer, and a butyl acrylate notexceeding about 60% of the interpolymer in the production ofshrinkproofing treatments utilizing baths of the character set forthabove. Anysuch compositions and baths and treatments may be employed inthis phase of the invention of the present case.

In application Serial No. 613,200, filed August 28, 1945, entitledElastomer production and utilization, now Patent 2,447,877, there isparticularly claimed the production of shrinkproofed wool by theutilization of copolymers of butadiene-1.3 and a Z-methyl but'adiene-L3,specifically isoprene and 2.3 dimethyl butadiene-L3, the copolymer beingin the cross-linked condition as set forth above in which it isunsuitable for utilization for rubber but in its crumbly condition asutilizable in accordance with the shrinkprooiing operations isparticularly important for the treatment of wool. Such materials aredescribed and claimed as employed in treating baths of the character setforth above. Any ofsuch materials may be employed in accordance with thepresent invention for that phase of'the treatment which includes the useof the polymer. Desirably as set forth in that prior case, the copolymerof butadiene-l.3 with isoprene is in the ratio of from 9:1 to 1:4 partsby weight, while that of the copolymer of butadiene with 2.3 dimethylbutadiene 1.3 is in the ratio desirably of 9:1 to 3:7- parts by weight.Such materials may be employed in the present inven- 9 tion.

atoms such as styrene and its derivatives, namely,

alpha, gamma-dimethyl styrene and dichlorostyrene as well asphenylacetylene, where the copolymers are more particularly of thecrosslinked character and if deposited per se from the emulsions wouldbe crumbly materials unsuitable. for rubber purposes. As set forth insuch case, baths employing such materials of the character as set forthabove may be utilized particularly where in the styrene copolymer, theamount of styrene does not exceed about-60% by v weight of thecopolymer, with the alpha. gamma-dimethyl styrene it does not exceedabout 40% oi the copolymer, whereas the dichlorostyrene does not exceedabout 40% of the weight of the copolymer, but for phenylacetylenepreferably not more than 20% by weight of the copolymer is present. Anyof those materials may be utilized as the polymer phase of the presentinvention.

In application Serial No. 615,097, filed September 7, 1945, entitledShrinkproofing wool and materials therefor, there is more particularlydescribed and claimed the shrinkproofing of wool 20 by the utilizationof cross-linked copolymers of a butadiene-1.3 and an unsaturated ketonecontaining not more than 12 carbon atoms, having the formulaCH2=CRa-CO.R3, where R: is selected from the group consisting ofhydrogen, alkyl and aryl groups, and R3 is selected from the groupconsisting of alkyl and aryl groups, including more particularlycopolymers of butadiene-1.3 with isopropenyl methyl ketone, methylenen-amyl methyl ketone, methylene isobutyl methyl ketone, etc., and wheremore particularly for shrinkproofing purposes in such copolymers theamount of isopropenyl methyl ketone does not exceed about 30 by weightof the copolymer, where methylene n-amyl methyl ketone is thecopolymerizing material it does not exceed about 40% by weight of thecopolymer, and when methylene isobutyl methyl ketone is thecopolymerizing material, it does not exceed about 20% of the copolymer.Such materials may be utilized in emulsions, dispersions and baths asmore particularly set forth above. Any such materials may be utilizedasthe polymer phase of the present invention.

In application Serial No. 615,098, filed September 7, 1945, entitledWoolshrinking copolymers, there is more particularly described andclaimed the utilization of cross-linked copolymers of a butadiene-1.3and an acrylonitrile, such as acrylonitrile itself, methacrylonitrile,etc., more particularly where the weight of the acrylonitrile materialeither acrylonitrile per se or methacrylonitrile does not exceed about40% by weight of the, copolymer, such copolymers particularly beingutilized in the cross-linked condition and employed in baths, aqueousemulsions and dispersions as set forth above. Any such materials may beutilized in the present invention for the polymer phase thereof.

In application Serial No. 631,483, filed November 28, 1945, entitledElastomeric copolymers and their utilization, there is more particularlydescribed and claimed the treatment of wool for shrinkproofin wherethere is utilized a copolymer of a butadiene-1.3 and a vinyl ester'whichpolymerizes to a hard resinous material, more particularly such estersas vinyl acetate and vinyl chloride, desirably the vinyl acetate whenemployed not exceeding about 40% by weight of the copolymer, and thevinyl chloride also notexceeding about 40% by weight of the copolymerwhen it is employed. Such materials may be utilized in theshrinkproofing of woolby employment in aqueous baths, dispersions andemulsions as set forth above. Any such materials may be er phase of thepresent inchloroprene polymer, either alone or with limited amounts ofother materials such as not exceeding about 50% of ethyl acrylatepolymer based on the total weight of polymers present, or a vegetableoil factice not exceeding about 40% by weight of the polymer togetherwith factice, or with methyl methacrylate polymer not exceeding about40% of the total weight of polymers when this is used, or where thechloroprene polymer is utilized with a synthetic butadiene-1.3 polymer,or with a natural rubber latex, the latter, however, not exceeding about75% of the total weight of polymer together with the latex present. Anyof these materials may be employed in the shrinkprooflng of wool in theform of baths dispersions and emulsions as set forth above. Thechloroprene polymer may also be utilized in the form of copolymers suchas with an acrylonltrile where the latter does not exceed about of thetotal weight of the polymers present or with an ethyl acrylatecopolymer, where the latter does not exceed about of the total weight ofthe polymers present, or of a methacrylate polymer not exceeding about40% of the total weight of polymerspresent and again any of thesematerials employed in dispersions, emulsions or aqueous baths as setforthabove. Any of these combinations may be utilized in accordance with5 the present invention as .the polymer phase thereof.

In application Serial No. 603,406, filed July 5, 1945, entitled Textileandfiber treatment, compositions and methods, now Patent 2,447,772,

40 there is more particularly described and claimed the utilization ofbutadiene-1.3 polymers and combinations thereof with other materials asin aqueous baths, dispersions and emulsions for the shrinkproofing ofwool where the butadiene com- 45 ponent, that is, the syntheticbutadiene polymer is employed in the form of a prevulcanized orpreoxidized material, where the treatment has been carried to a point sothat the polymer is present in a condition in which it will not give a 5tacky deposit on fibers treated therewith. It is in substantiallyinsoluble condition although it will swell with organic solvents as setforth" above. Such prevulcanized or oxygen treated polymer emulsions,baths and dispersions may be employed in accordance with the presentinvention. Furthermore as set forth in that case and in other companioncases, antioxidants may be present not only to control any furtheroxidation or vulcanization which takes place and to check the latter,but also because it has been "found that antioxidants exert a veryfavorable effect of unexpected character on the shrinkproofing obtained.Thus antioxidants of the usual type may be employed in'the dispersionsor 5 emulsions in order to obtain the effects set forth above and anysuch materials may be utilized in accordance with the present inventionas the polymer phase thereof.

Accordingly, in accordance with the present invention, wool ofsubstantially normal hand is obtained but which has been shrinkproofedwith a synthetic butadiene-1.3 polymer which may be of any of thecharacters set forth above, either by itself or copolymers of thecharacter described above, utilized, however, in combination with acured urea-formaldehyde type resin. The amounts of polymer plus resinpresent in the treated material may vary from about 1 to 50% on theweight of the wool. Varying ratios of polymer to resin may be used, butin order to secure satisfactory shrinkage control, between 2 and 15% ofpolymer, based on the weight of the wool, should be utilized. Apreferred ratio with urea formaldehyde resins varying from about 4-21 ofurea formaldehyde type resin to polybutadiene to 1:12 of such resin topolybutadiene. Or preferred ratios with melamine type materials may runfrom about 3.121 of the melamine type resin to polybutadiene to 1:12 ofthe melamine or alkylated melamine type material. In all such caseswhere shrinkproofing is obtained, the amount of the polymer presentshould be generally at least 1% on the weight of the wool and. theamount of any other materials present should not interfere with theshrinkproofing sought while other desired characteristics may beenhanced as pointed out above by the presence of such added materials.

The following examples illustrate the invention, the parts being byweight unless otherwise set forth.

Example 1.A condensation product of ureaformaldehyde as well asbutadiene polymer emul-e sion was applied to swatches of wool flannel,measuring 10" X 10" in size. The samples were immersed in the resinsolution first and the excess pad liquor was removed by passing thefabric through squeeze rollers. The weight of the wool samples was notedbefore and after padding and from the weight increase the amount ofresin applied to the fabric was calculated. The samples were dried at 60C. and cured at this temperature for 12 hours. After curing thepolybutadiene dispersion was applied in the same manner and the amountof polymer on the fabric was calculated as outlined above.

The solution of the urea-formaldehyde condensation product was preparedby dissolving equimolecular quantities of dlmethylolurea and urea insufficient water to form a solution containing 10% solids. To this wasadded 5% of ammonium sulfate based on the weight of the solids.

The aqueous polybutadien-e dispersion was prepared as follows: butadienewas passed over calcium chloride and condensed in a pressure re-' actorcooled to below 5 C. parts of butadiene were then weighed out in thereactor. While the reactor was kept in the freezing mixture, thefollowing solution was added. 6 parts of soap (Ivory Flakes) wasdissolved in 125 parts of water and the pH of the water-soap solutionwas adjusted to 10 by the addition of a small amount of 5% sodiumhydroxide solution. The following catalysts and regulators were thenadded to the soap solution, 0.1 part of dodecyl mercaptan, 0.01 part ofpotassium ferricyanide, 0.2 parts of potassium persulfate. The reactorwas then closed, allowed to come to room temperature and put in anagitator with a constant temperature bath at 45 C.

After 16 hours, the reaction was substantially complete as indicated bya very slight pressure within the reactor. The emulsion was thensubjected to a vacuum of approximately 15 pounds per square inch to drawoff the small amount of monomer gases that may be present. The polymeremulsion was then given an oxidation treatment as follows: added 1% ofthe sodium salt of sulfonated oleyl alcohol and 2% of a 30% hydrogenperoxide solution, then heated for one hour, the temperature risinggradually to 200 F. Since polymerization was almost complete, it wasassumed that this dispersion contained 25% of polybutadiene.

This emulsion was diluted with water so that it contained 6%polybutadiene.

Four lengths of 8" each were marked on each sample, two in the directionof the warp and two in the direction of the fill. From thesemeasurements the area in square inches was calculated. The wool sampleswere then washed for three hours in a mechanical washing machine, afterwhich laundering they were rinsed, dried and remeasured.

The amount of resin and polybutadiene deposited on the fabric as well asthe area shrinkage are shown below.

Percent Urea- The finished swatches had a dry, normal hand and thepieces which contained the urea-formaldehyde resin exhibited superiordraping qualities.

Example 2.--A solution was made from equimolecular quantities ofdimethylolurea and urea. The solution was diluted to a point where itcontained 10% solids, to which was added 5% of ammonium sulfate, basedon the weight of the solids. Four swatches of flannel were measuredaccurately and the area was calculated, after which they were thoroughlywet out with the urea-formaldehyde solution. The amount of liquidpick-up was determined by weighing the wool samples before wetting andafter the excess pad liquor had been removed by passing the swatchesthrough squeeze rollers. Of the samples, two were cured for 10 minutesat C. and two were cured for 12 hours at 60 C.

()ne piece-each, cured at a low and at a high temperature, as well as anuntreated piece of flannel were then immersed in a polybutadienedispersion, and after complete wetting out had taken place, the excesswas removed by passing the goods through squeeze rollers, therebyremoving the excess pad liquor. The polybutadiene solution was similarto the one used in the previous example, and the amount of solidsdeposited on the fabric was calculated as outlined above.

After drying, the samples were given a threehour laundering. The amountof shrinkage, as well as a resume of the treatment which was given tothe fabric may be found in the table below.

Per Cent Per Cent Urea-formal- Polybuggg Sample No. dchyde Cure tadleneShrink Resin on on Fabric Fabric age l7 12 hrs. 60 0--.- 6 4.2 l7 10min. 125 6 4. 6 17 12 hrs. 60 C 23.1 I l7 10 min. 125' C-.. 29. 9 5 6 5.2 6 Untreated. 24. 0

The flannel had retained its original desirable hand and the drapingcharacteristics of the ureaformaldehyde containing fabrics was greatlyenhanced.

Example 3.-A set of samples was prepared exactly as described in Example2 except that 15% urea-formaldehyde condensation product Example 4.A setof samples was prepared exactly as described in Example 2 except that12% urea-formaldehyde condensation product was applied to the fabricinstead of 17%.

A firm hand was imparted to the fabric. The samples which were treatedwith the poly'butadiene emulsion showed superior resistance to feltingand shrinkage on laundering.

The results of a three-hour wash best are given herewith.

Per Cent Per Cent Urea-formal- Polybuigs Sample No. dehyde Cure tadieneshrimp Resin on on 9 Fabric Fabric 88 1 12 12 hrs. 60 6 5. 4 2 12 10min. 125 6 4. 9 3 12 12 hrs. 60 0.--- 27.4 4 12 10 min. 125 0. 29.1 6 66. 6 Untreated- 31. 0

Example 5.'A treating bath was prepared by dissolving 120 partsdimethylolurea and'30 parts of urea in 850 parts of water. To thissolution was added ammonium sulfate, based on the weight of theurea-formaldehyde condensation product and 2% sodium lauryl sulfatebased on the total weight of the pad liquor. Wool flannel squares 10" x10" in size were weighted and immersed in the liquor. After thoroughpenetration had taken place the excess liquor was removed by passing thefabric through squeeze rollers. The goods were weighed again and fromthe weight increase as well as the strength of the solution the amountof urea-formaldehyde on the fabric was calculated. After drying, twoswatches were cured at 125 C. for ten minutes while the other two werecured for twelve hours at 60 C.

One piece each cured at 60 C. and at 125 C. were treated with thepolybutadiene emulsion of Example 1, as follows:

. 12 The samples were rinsed with warm water and dried.

A piece of wool to which no urea-formaldehyde had been applied was alsotreated with the polybutadiene emulsion according to the procedure asoutlined above.

All samples, as well as an untreated swatch were washedfor three hoursin a washing machine, containing 35 parts of powdered neutral treated.

soap in 18,500 parts of water at 65 C. After rinsing and drying thesamples were remeasured. The results have been tabulated below. v

Per Cent Polybutadiene on Fabric Per Cent Area Shrinkage Sample N o.Cure The urea-formaldehyde treated fabrics had superior drapingqualities.

Example 6.-A set of samples was prepared exactly as described in theprevious example with the exception that only 14% of theurea-formaldehyde condensation product was applied instead of 20%. v

The fabrics had good draping qualities and. good shrink resistance, aswell as superior 'resistance to felting. The degree of felting, etc.occurring after a three-hour laundering is tabulated below.

Percent Pol butad sue on Fabric Degree oi Sample No. Felting RODS.

s ht. considerable.

. o. 5 slight. U n considerable.

Example--7.A similar set of samples was prepared and tested but in thiscase only 10% ureaformaldeh'yde condensation product was applied to thefabric. In all otherrespects the procedure was identical to the one usedin Example 5.

Excellent draping eifects were imparted to the I treated fabrics, aswell as good shrink resistance The two pieces of wool weighing 24.2parts were put into a bath consisting of 485 parts of water at -'70 C.and 4.8 parts of 50% acetic acid. After five minutes, 4.8 parts of thepolybutadiene emulsion was added, this amount containing a weight ofpolymer corresponding to 6% of the weight of the samples. Five minuteslater 2.4 parts of anhydrous sodium sulfate in the form of a 10%solution were added and these additions were repeated until the bathcleared completely, indicating complete exhaustion. The

samples had been agitated continuously throughout the application, andthe temperature kept between and C.

to the samples to which polybutadiene had been applied.

Percent Urea-formaldehyde Resin on Fabric Percent Polybutadiene onFabric Sample De of N o. Fst i g slight.

Do. considerable.

Do. none. considerable.

Example 8.-Three squares of wool flannel, measuring 10" x 10" weretreated with 5% polybutadiene dispersion according to the procedureoutlined in Example 5.

After rinsing and drying one sample was immersed in a 10% aqueousalkylated melamine formaldehyde solution. This solution was preaccusesulfate was added to the urea-formaldehydesolution. Both percentageswere based on the weight of the solids present in the solutions.

After complete penetration had taken place The area shrinkage was asfollows:

Area t? Treated with Shrinkage Per cent 6% polybutadiene+l% Resloom" 0.7 6% polybutadiene+10% urea-formaldehyde 1. 6% polybutadiene 6. 4 10% R00111" 11.2 10% urea-formaldehyde- 30. 6 Con 31. 1

Example Ili -Samples of wool flannel were the excess liquor was removedby passing the treated with aqueous alkylated melamine form aldehydesolutions, prepared from a commercial Samples through squeeze i Afterdrying product known to the trade as Resloom M75 iifistfffiliifnfiffifi.iiiitdtiififuttstt This 55% was h t i th 1 n thdiluted with water so as to form solutions which as mm t 6 q i 0 6 so ue contained 19, 14, 10 and 5% solids and to which amount of resindeposited on the fabric was 3% of diammomum phosphate based on thedetermmed; weight of the solids, had been added. The ex- Two additionalpieces ofjlannel were treated v cess solution was removed by passingthrough m the Same manner wlth and squeeze rollers, the fabric retaining100% of its formaldehyde solutions without having had the weight ofsolution After drying an samples polybutadiene treatment first. werecured for ten minutes at 125 C.

All pieces as well as an untreated piece were A similar Set f sampleswas prepared and washed for three hours in a mechanical washing ftcuring these Swatches were immersed m machine- After drying they wereremeasured a solution which'had been obtained by diluting and the ar arin a was calculatedan aqueous polybutadiene dispersion with water Arsum of the vari tr m t as Well to such an extent, that the resultingsolution as the area shrinkage is givenherewith. contained 6% of thepolymer. The samples pPergertit P C R T PeiCent sampleNoeat: one "meastas that.

Fabric age 1 5 10m1n.125 9%Res1oom 0.9 g 5 10 min. 125 C 10.8%urea-formaldehyde g 411 163%15516651 1111: 2016 5. 11.0%ureaformaldehyde. 23. 3 fiUntreated 24.6

Example 9.Five solutions were made up as Alkylated Melamine formaldehyde(Resloom M75 solids) 18.2 18.2

Urea formaldehyde condensation product 15% solids 66.7 66.7 Diammoniumphosphate .3 .3 Ammonium sulfate .5 .5 67.5 88 76 81.5 32.8

Watch--.

1 The urea formaldehyde condensation product-solution was prepared bydissolving equimolecular quantities of dlmethylol urea and urea insufficient water to yield a solution containing a total of 15% solids.

Measured swatches of wool were thoroughly wet out, the excess liquorremoved by passing the fabric through squeeze rollers, and the amount ofliquid pick-up determined. From the pick-up, the amount of polymerand/or resin deposited on the wool was calculated. These amounts as wellas the shrinkage may be found inthe table below. The pieces were dried,and those containing the urea-formaldehyde and the alkylated melamineformaldehyde condensation products were cured for ten minutes at 125 C.After curing, these pieces had a normal, full hand and pleasing drapingcharacteristics.

All pieces, including an untreated piece, were washed for three hoursand. remeasured.

were permitted to remain in contact with the bath until they werecompletely wetted out. The excess liquid was then removed by passing theswatches through squeeze rollers.

The samples were found to have doubled in weight, and since the padliquor contained 6% of polymer, 6% polybutadiene was deposited on thefabric.

All samples were measured before and after laundering and the percentarea shrinkage was determined. The results were as follows:

Area kjf" Treated with Shrinkage Per cent 19% alkylated melamineformaldehyde 10. 5 19% alkylated melamine formaldehyde+6% 4.5

polybutadiene. 14% alkylated melamine formaldehyde 17. 9 14% alkylatedmelamine formaldehyde+6% 4.2

polybutadiene. 10% alkylated melamine formaldehyde 2i. 0 3a 10%alkylated melamine'formaldehyde-Hi9, 4.2

polybutadiene. 4 5% alkylated melamine formaldehyde 23. 3 4a 5%alkylated melamine formaldehyde+6% 6.7

polybutadiene. 5 Untreated 80.1

Example 11.A solution of a melamine-formaldehyde condensation productwas prepared by dissolving with heat melamine and formaldehyde in amolar ratio of 1 to 3 in sufficient water to above.

acemes give a product containing 10% solids. Qn cooling of ammoniumsulfate based on the weight of the solids was added as a catalyst.

Two swatches of wool x 10" were weighed andimmersed in this solution.After the samples had wetted out thoroughly. the excess solution wasremoved by passing them through squeeac The samples were reweighed,dried and rollers. cured by allowing them to remain at room temperaturefor 24 hours.

The solution was then diluted with water soas to contain 5%melamine-formaldehyde condensation product and an additional two sampleswere heated according the procedure as outlined In each case the fabricincreased 100% in weight.

After the curing one sample each containing 1.0% and 5% of melamineformaldehyde as well as an untreated swatch were treated with the 6%polybutadiene emulsion oi Example 1.

The emulsion .was applied by padding and in this manner 6% Dolybutadienewas deposited on the fabric. Thesamples. which included those which weretreated with melamine-formaldehyde only, as well as a measured untreatedswatch. were then dried and laundered for three hours.

After drying, the swatches were remeasured and;

the amount of area shrinkage was calculated in per cent;

control follows: y

Per Cent P Cent Per Cent Melamine- Po ybuta- Area Sample N o. ior mg lgeggda (em on swab Fabric 5 2;. t Y 5 3 i o'fl'fiir' 2a shrinkresistance were imparted to the fabric as tabulated below. 4

ufih th 1 S t. M

0 0 y ll rea dehydo Resin dlene on Shrinkon Fabric Fabric age 10 2a.: 10e as a 2a: 6 a a1 c 6.2 6 Untreated- 24. 4

Example 13.A solution of a melamine-formaldehyde condensation productwas prepared by dissolving with heat melamineand formaldehyde in amolarratlo of 1 to 4 in suflicient water to give -a product containing10% solids. After the solusqueeze rollers, dried and cured for 24 hoursat v A rsum of the treatment and the shrinkage room temperature.

One of these wool squares was then padded from a 6% polybutadieneemulsion and permitted to dry. Another two swatches were treated with a10% solution of a melaminei'ormaldehyde condensation product prepared bydissolving melamine and formaldehyde condensation product preparedbydissolving melamine and formaldehyde'in' a molar ratio of 1 to 3. Nocatalyst was added to this solution. The treated wool pieces were curedfor 24 hours at room temperature.

One of these pieces was also treated with 6% polybutadiene and dried.Finally all these swatches, as well as a swatch of wool treated with 6%polybutadiene and an untreated square were washed and measured forshrinkage control. A good full hand was imparted to the fabric which hadexcellent draping qualities.

. Per cent Polybutadiene on Fabric Per cent Catalyst Area I ShrinkageThe samples which were treated with the melamine-formaldehyde resin hada desirable drape and a full-hand.

Example 12.A similar set of samples was preterlstics, and in someinstances good felting and Having thus set forth my invention, I claim:

i l bath for shrinkproofing wool while retaining substantially normalhand which comprises an aqueoussubstantially stable emulsion containinga synthetic butadiene-1.3 polymer of polymerization and at least one ofthe ureaformaldehyde and melamine-formaldehyde resins, the ratio ofresin to polymer being from 4:1 to 1:12 for the urea-formaldehyde resinand from 3.1:1'to 1:12 for the melamine-formaldehyde resin, the polymerand resin being present,

17 in amount to give 1 to 50% by weight of polymer and resin depositionon the wool, the amount of polymer being from 2 to 15% by weight on thewool, the bath also containing a non-cationic emulsifying agent and atleast 25% by weight on the polymer of a water-soluble neutral salt of analkali metal as conditioning electrolyte and having a pH below about 7.l

2. A bath as set forth in claim 1, in which the emulsifying agent isanionic.

3. A .bath as set forth in claim 1, which ineludes a curing catalyst forthe resin.

4. A bath as set forth in claim 1, in which the resin is aurea-formaldehyde resin and the resin to polymer ratio is from 4:1 to1:12.

5. A bath as set forth in claim 1, in which the resin is amelamine-formaldehyde resin and the resin to polymer ratio is from 3.1:1to 1:12.

' JOHN B. .RUST.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,173,242 Young 1 Sept. 19, 19392,211,959 Maney Aug. 20, 1940 2,299,786 Battye et a1 Oct. 27, 19422,340,358 Young Feb. 1, 1944 2,384,880 Britton et a1. Sept. 18, 19452,405,038 Jennings July so, 1946 OTHER REFERENCES Rubber Age (N. Y.)V01. 48 of 1940, DD- 23-25.

